Cationic surface-active agents

ABSTRACT

Cationic surface-active agents which are polyhydroxylated tertiary amines or the quaternary ammonium salts thereof and which are usefully employed in cosmetic compositions, are prepared by condensing on a fatty alcohol, glycerol epihalohydrin alone or together with an epoxide to form polyhalogenated polyethers, which in turn are converted to polyhalogenated glycidyl ethers, the latter being reacted with a secondary amine to form polyhalogenated tertiary amines which are then reacted with sodium or potassium acetate in the presence of a diol to form said polyhydroxylated tertiary amines.

United States Patent I 1 Kalopissis et al.

[4 1 Apr. 22, 1975 [22] Filed:

[73] Assignee: Societe Anonyme dite: L'Oreal, Paris, France Oct. 6, 1971 [21] Appl. No.: 187,151

Related US. Application Data [63] Continuation-impart of Ser. No. 655.336, July 24,

1967, abandoned.

[52] US. Cl... 260/584 C; 260/5705 R; 260/584 B; 260/2477 A; 260/5676 M; 260/247.7 C; 260/293.83; 260/297; 424/8; 424/10.l;

[51] Int. Cl. C07c 93/02 [58] Field of Search 260/583 R, 584 C [56] References Cited UNITED STATES PATENTS 3,366,632 H1968 Wakeman et al. 260/584 C 3.449.430 6/1969 Dohr 260/583 R Primary Examiner-Lewis Gotts Assistant Examiner-D. R. Phillips Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACT Cationic surface-active agents which are polyhydroxylated tertiary amines or the quaternary ammonium salts thereof and which are usefully employed in cosmetic compositions, are prepared by condensing on a fatty alcohol, glycerol epihalohydrin alone or together with an epoxide to form polyhalogenated polyethers, which in turn are converted to polyhalogenated glycidyl ethers, the latter being reacted with a secondary amine to form polyhalogenated tertiary amines which are then reacted with sodium or potassium acetate in the presence of a diol to form said polyhydroxylated tertiary amines.

22 Claims, No Drawings 1 2 CATIONIC SURFACE-ACTIVE AGENTS having the formula ROH wherein R has the meaning This application is a continuation-in-part of our eargiven above (n+1) moles of glycerol epihalohydrin lier application Ser. No. 655,336 filed July 24, 1967, having the formula now abandoned.

The present invention relates to cationic surface ac- 5 CH H-CH X tive agents which are the condensation products of an 0/ alcohol having the formula ROH with (a) glycerol epihaiohydrin or (b) an epoxide and glycerol epihalohy' wherein n has the meaning given above and X is halogen, preferably chlorine or bromine to form a mixture of l h l n ted ol ethers havin the formula I. Surface Active A ents Which Are The Condensation p0 y a oge a P y g Product Of An Al ohol And Glycerol Epihalohydrin i? b. dehydrohalogenatmg said polyhalogenated polyln accordance wlth thls embodiment of the pmsent ethers from step (a) with an alkali metal hydroxide or invention there is Provided cationic Surface active an alkaline earth metal hydroxide to form a mixture of agents Selected from the group consisting of polyhalogenated glycidyl ethers having the formula 1. agents having the formula g I) O which are hydroxylated condensation products of an alcohol having the formula ROH and glycerol epihalohydrin wherein R is a hydrophilic group selected from Teactlffg h po yhalogenated glycidyl ethers from the class consisting of linear or branched alkyl and al- Step (b) wlth a secondary aKnme to f a mixture of kenyl having 8-22 carbon atoms, and alkylphenyl havpolyhalogenated tertiary amines having the formula ing 8-22 carbon atoms, R and R each independently are selected from the group consisting of lower alkyl having 1-4 carbon atoms and hydroxy lower alkyl hav- 1/ ing 1-4 carbon atoms or together with the nitrogen a C T 1 atom to which they are attached form a ring selected RO+C2H3(CH2X)O n H2 CHOH CR2 from the group consisting of morpholine and piperidine 2 and n is 05-10; and

2. agents which are the quaternary ammonium salts of (1) having the formula 5 R RO'-EC H (CH OH)O -CH -CHOHCH N Y (II) l R R 2 where n, R, R and R have the meaning given above, nd R is selected from the group consisting of methyl and (1. replacing the halogen by a hydroxyl in the polyethyl, and Y is an anion selected from the group conhalogenated tertiary amines from step (c) to form a sisting of Cl, Br, I, SO CH SO C I-I CH SO and mixture of polyhydroxylated tertiary amines having formula (I) given above.

CH go The various steps in the above process for preparing 3 3 the surface active agents represented by formula (I) are as follows:

(a) ROH (n+1) eye-on x ran-50 %(cn moa cn cnon-cn -x (III) (III) NaOH ROEC2H3(CH2X)O3ECH2CHCH? (Iv) NaX+H O;

l d (c) (IV) HN 1+ Ro-Ec n (cii x)o; ci1 CHOH CH N R2 (V) an (d) (v) RO[-C H (CH 0I-l)O-}-CH -CHOHCH -N (I).

+OH n \R2 The cationic surface active agents of this embodi- The quaternization of the surface active agents reprement of the invention are prepared by sented by formula I yields quaternary ammonium salts a. condensing on a fatty alcohol or on an alkyl phenol having the formula no-{j-c H (CH H)030H -CHOH-CH -N 1 wherein R, R R R Y and n have the meaning given above.

In the course of the condensation reaction (a) above,

when the epoxy ring is opened during the polycondensation, a mixture of compounds comprising the structures -cH -cn-o and -cn-cn'-ois obtained.

R a -cn-o n -CHOH-CH -N RI and 2 ca on n ,1 v n cn-cn -o cn -cnon-cn -rgf cn on n r and the corresponding two isomers of the quaternary ammonium salts.

In the above formulae n is defined by the equation:

(n+l) E wherein M is equal to the molecular weight of the alcohol or alkyl phenol ROI-I, E is equal to the molecular weight of the glycerol epihalohydrin and l is the hydroxyl index of the condensation product, i.e., the mixture of polyhalogenated polyethers represented by formula (III) above, after step (21).

During the condensation reaction (a) in which (n+l) moles of glycerol epihalohydrin are reacted on one mole of alcohol or alkyl phenol, the number of moles of glycerol epihalohydrin fixed by one mole of alcohol or alkyl phenyl to form the recurring units, [-C H (CH X)O]-, can be greater or smaller than the value of n and a mixture of compounds, all responding to the general formula III are formed, but in which the number of recurring units varies and all those different numbers are distributed statistically around a mean value represented by n. Consequently, n in the final product represents the mean value or the average statistical value of the number of recurring units, I-C l-I (CH OH)O-l-, fixed on the different compounds having the general formula I or II.

An important fact which should be emphasized and which constitutes one of the essential advantages of the process of preparing the surface-active agents of this invention is that the present process results in the formation of compounds having a single lipophilic chain per hydrophilic chain.

Moreover, the process of the present invention permits the regulation of the hydrophilic and lipophilic properties of the final product. The hydrophilic characteristic of the resulting surface active agents can be regulated by choosing the value of the number n of moles of glycerol epihalohydrin to be reacted with one mole of fatty alcohol or alkyl phenol. The lipophilic characteristic of the resulting surface active agents can be regulated by choosing the length of the hydrocarbon chain R in the fatty alcohol or alkyl phenol used as an initial reactant.

The following is a detailed description of a preferred embodiment of producing the above surface-active agents.

In step (a), the condensation of glycerol epichlorohydrin or glycerol epibromohydrin on the fatty alcohol or alkyl phenol is carried out in the presence of an acid catalyst, such as boron trifluoride, stannic chloride or antimony pentachloride, at a temperature between 25-160C. Preferably boron trifluoride is employed at a temperature between 60120C. The proportion of BF;, with respect to the total mass of reactants ranges between 0.10.2 weight In step (b), the polyhalogenated polyethers, represented by formula (III) above, which result from step (a), are converted to glycidyl ethers (Formula IV) by dehydrohalogenation of the halohydrin, using an aqueous solution of an alkali or alkaline earth metal hydroxide, having a concentration, by weight, of from 2050%. The molar ratio of alkali or alkaline earth metal hydroxide to polyhalogenated polyether ranges between 1:1 to 1:2 and preferably between 1:12 to 1:15. During this phase of the overall process, which ordinarily is initially conducted at about 20C or ambient temperature, the reaction temperature rises to about C. When the exotherrnicity of the reaction ceases, the reaction is terminated by heating the reaction mixture in a water bath. This dehydrohalogenation operation is generally conducted in the presence of a solvent to obtain high reaction speeds and high epoxidation yields. The solvent employed should, preferably, not be miscible with concentrated aqueous solutions of electrolytes so that the resulting polyhalogenated glycidyl ethers can be separated from the reaction medium simply by decantation. Tertiary butyl alcohol and 2- butoxy ethanol are particularly useful solvents when used in weight proportions essentially equal to that of the halohydrin to be dehydrohalogenated. Quaternary ammonium salts comprising a lipophilic chain can be used to improve the contact between the reactants. The resulting polyhalogenated glycidyl ether, if desired, can be isolated by evaporation of the solvent or it can be used in solution in the subsequent stage, i.e., step (c).

In step (c), the polyhalogenated glycidyl ethers from step (b) are reacted with a secondary amine at a tem-I perature from 25l20C to open the epoxide ring and;

thereby form the polyhalogenated tertiary amines hav-= ing formula (IV).

Alternatively, the polyhalogenated tertiary amines of formula (IV) can be prepared in a single step by reacting the polyhalogenated polyethers from step (a) with. a secondary amine in the presence of an alkali or alkaline earth metal hydroxide. f

Representative secondary amines usefully employedi in the present invention include diethylamine, di-t propylamine, morpholine, piperidine and alkanola-j mines such as diethanolamine, diisopropanolamine, diglycerylamine and N-ethylethanolamine.

The molar ratio of secondary amine to polyhalogenated glycidyl ether in step (c) or the ratio of secondary amine to polyhalogenated polyether (when the alternate route is practiced) to produce polyhalogenated tertiary amines is between about 1:1 to 121.5 and, preferably, about 1:12.

In step (d), the replacement of the halogen by a hydroxyl in the polyhalogenated tertiary amine from step (c), or from its alternate route, yields the polyhydroxylated amines of the present invention which are useful surface active agents and which are represented by formula I. This operation is carried out with an alkaline salt of a carboxylic acid, such as sodium or potassium acetate, at a temperature between l50-200C, preferably about 180C, in the presence or absence of a solvent.

The presence of a solvent in the reaction medium during step (d) assures both instantaneous and progressive contact among the reactants and easy separation therefrom of the mineral halide formed. Suitable solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol as well as the monoalkylethers of these diols such as, monobutyl ether of ethylene glycol and monobutyl ether of diethylene glycol. The hydroxylated solvents also intervene by alcoholysis of the esters formed in an intermediate step.

When the reaction is carried out in the absence of a solvent, as may be the case when the alkaline salt of carboxylic acid is somewhat soluble in the reaction medium, the polyhydroxylated tertiary amine is obtained by alcoholysis of the esters of carboxylic acid with a lower alcohol such as methanol or ethanol, or by saponification followed by salting out or extraction.

In one preferred commercial exploitation of the present invention, the polyhalogenated polyethers from step (a) are reacted with a secondary amine, as defined above, in the presence of an alkali or alkaline earth metal hydrooxide, without isolating the glycidyl ethers thus formed. After reaction with an alkaline salt of carboxylic acid, the esterified amino ethers are separated from the mineral halide by filtration or washing, and then the salts of carboxylic acid are regenerated in situ from the carboxylic esters by saponification with an alkaline hydroxide. Thus, the alkaline salt of carboxylic acid is recovered in aqueous solution and can be used for another hydroxylation reaction.

As stated above, the surface-active agents of this embodiment of the present invention also include the quaternary ammonium salts of the compounds represented by formula I, the quaternary ammonium salts being represented by formula II. To produce said quaternary ammonium salts, the compounds represented by formula I can be reacted with, for instance a quaternizing agent such as methyl sulfate, ethyl sulfate, ethyl chloride, ethyl bromide, methyl iodide, methyl paratoluylene sulfate or methyl methane sulfonate. The mole ratio of quaternizing agent to the compounds repreand derivatives thereof.

Additionally, the process of the present invention yields stable surface-active agents which are soluble in water over a very wide pH range. The present process also provides surface-active agents which are soluble in concentrated sodium hydroxide without risk of instability which occurs, for example, with the quaternary ammonium hydroxides. Moreover, this result is obtained without the introduction of supplementary ionic groups, and especially anionic groups, which impair the substantive characteristics of the surface-active agents. The solubility characteristics of the surface-active agents of this invention are, of course, highly variable as a function of the values of n, R, R and R Certain of these agents in which R represents alkyl or alkaryl and in which n is equal to 5-6 are soluble in sodium hydroxide. The extent to which these surface-active agents may irritate the skin and mucous membranes is also dependent on the values of n, R, R and R In general, however, the surface-active agents of this invention are clearly less irritating than fatty amines and their derivatives.

The surface active agents of the present invention also provide advantages not secured by such prior art compounds as those disclosed in Luxembourg application No. 48,458 filed Apr. 23, 1965 which are nonionic surface-active agents having the formula In contradistinction, the surface-active agents of the present invention contain a hydroxy amino propane group which imparts thereto their cationic characteristics and their substantivity, i.e., their affinity for fibers and particularly for animal and vegetable fibers.

The surface-active agents of the present invention also compare favorably with amino polyethers having the formula and the substitution of a -[-C H (CH OI-I)O}- group for the oxyethylene group (-OCI-I CH is very useful.

The surface-active agents of this embodiment of the present invention because of their physical and chemical characteristics are suitably employed in cosmetic preparations, and particularly in shampoo, hair dyes hair rinses and permanent waving compositions. Further when the surface-active agents of this embodiment of the present invention, are used in compositions for treating hair, they impart to the hair a certain sheen and a pleasing texture. The hair is particularly soft, odorless and is easily untangled.

Thus, in accordance with the present invention there is provided a shampoo composition comprising an aqueous solution of the surface-active agents of this invention present in amounts of about 0.5 to 10% by weight of said shampoo composition, having a pH ranging from about 3 to 6.5. The pH can be adjusted to the desired value by incorporating into said composition an acidic component such as an organic acid including lactic, acetic or citric acid and the like.

In another embodiment of the present invention hair is permanently waved by applying to the hair wound on curlers during the first stage, i.e., during the reducing stage, a composition comprising reducing agent, permitting the composition to remain on the hair for a time sufficient to alter the disulphide bonds of the keratin of the hair, generally about -40 minutes, thoroughly rinsing the hair to remove residual reducing agent and applying in the second stage, i.e., during the neutralization stage, a cosmetic composition comprising a mixture of an oxidizing or neutralizing agent and the surface-active agent of the present invention, whereby the disulphide bonds of the keratin of the hair are reformed.

Conventional reducing agents employed are advantageously those organic thiols which are generally used to perform the first stage of a permanent waving operation. Representative thiols include thioglycolic acid and its salts, glycol thioglycolate, glycerol thioglycolate, thioglycolic amide, thiolactic acid, glycol thiolactate, B-mercaptoethanol, N-carboxymethyl mercapto acetamid, B-mercapto propionic acid and the like. Generally the composition comprising the reducing agent is an aqueous solution of said reducing agent present in amounts of about 2 to by weight thereof and having a pH ranging from about 8 to 10.

The neutralizing composition of the present invention comprises an aqueous solution of 0,5 to 4 weight percent of a conventional neutralizing or oxidizing agent and about 0,2 to 5 weight percent of the surface active agent of this invention. Conventional neutralizing agents employed include, for instance, hydrogen peroxide, sodium or potassium bromate, sodium perborate or percarbonate and the like.

The surface-active agents of the present invention are also usefully employed in hair dye compositions comprising a solution in a solvent selected from the group consisting of water, an aqueous solution of a lower alkanol such as ethanol and isopropanol, of a glycol such as butyl glycol, propylene glycol, ethylene glycol, 3-amyloxy 4-propane 1,2-dio1, and of ethers of glycol such as monobutyl ether of ethylene glycol wherein said alkanol and/or glycol and/or ether of glycol is present in amounts of about 8 to 25% by weight of said solution, a hair dye such as azo, anthraquinone and nitro dyes of the benzene series, and 0,5 to 6 percent by weight of the surface-active agent of the present invention.

Additionally, if desired, said hair dye composition can include its weight of 6% hydrogen peroxide to provide said composition in gel form.

Generally the dye is present in amounts of about 0,1 to 5 percent by weight of said composition which has a pH ranging from about 8 to 10,5.

Representative dyes include paraphenylene diamine, 2,5-toluene diamine sulfate, chloroparaphenylene diamine sulfate, nitroparaphenylene diamine, 1,2,4- triaminobenzene trihydrochloride, paraaminodiphenyl amine, ortho phenylene diamine, 4-chloro ortho phenylene diamine, 4-nitro ortho phenylene diamine, paraaminophenol, 4-amino 2-methyl phenol sulfate, 4-amino-3-methyl phenol, 4-amino 2-nitro phenol, mdiamino anisol and its sulfate, p-aminophenol and its sulfate, nitro-p-phenylene diamine, p-toluylene diamine, resorcine, hydroquinone, 3-nitro 4-6- aminoethylamino anisole hydrochloride, 2-4- -diaminophenol hydrochloride, paramethyl aminophe- 8 nol sulfate, ortho aminophenol, 4-chloro 2- aminophenol, 4-nitro 2-aminophenol, S-nitro 2- aminophenol, 4,6-dinitro 2-aminophenol, 6-chloro 4- nitro Z-aminophenol hydrochloride, 4-amino diphenylamine, 4,4-diamino diphenylamine sulfate, metaphenylene diamine, chloro-meta phenylene diamine, nitrometa phenylene diamine, meta toluylene diamine, 2,4- diamino anisol sulfate, meta aminophenol, 3,5- diaminophenol hydrochloride, diethyl meta aminophenol, paraamino ortho cresol, l-dimethylamino 3-amino ethylamino 4-nitro benzene, l-hydroxy-2,4-di(p-trimethylammoniumphenylamino) anthraquinone methosulfate, l-hydroxy-2,4-di (p-trimethyl ammoniumphenylamino) anthraquinone iodide, 1- amino propylamino anthraquinone, 1,8-Bis-7- aminopropylamino anthraquinone, l-diethylamino 2- ethylamino-nitro-4-NN-dihydroxyethylamino benzene dihydrochloride, 4-N-methylamino-3-nitro-1-N-B- aminoethylamino benzene, [l-hydroxy-4-(y methylmorpholinium) propylamino anthraquinone]methyl sulfate, 2-,B-aminoethylaminoanthraquinone, 1,5-di-(l3- aminopropylamino) anthraquinone, l-methylamino-4- amino propylamino anthraquinone, l-amino propylamino-anthraquinone 1,4-diamino-5'y aminopropylaminc-anthraquinone. Additional examples of commercially available useful dyes include, as monoazo dyes, Cl Acid Blue 92 (13390) and Cl Acid Yellow 23 (19140); as diazo dyes, Cl Acid Orange 24 (20170); as triphenylmethane type dyes, Cl Acid Blue 1 (42045), Cl Acid Violet 19 (42685), Cl Acid Blue 22 (42755) and Cl Acid Violet 15 (43525); as xanthene dyes, C1 Acid Violet 9 (45190); as azine dyes, Cl Acid Black 2 (50420), Cl Acid Blue 59 (50315) and C1 Acid Blue 61 (50330); as anthraquinone dyes, Cl Acid Violet 43 (60730), Cl Acid Blue (61585), Cl Acid Violet 51 (62165) and Cl Acid Blue 138 (62075); as premetallized dyes, both 1:1 and 2:1 complexes, chromium and cobalt, for instance C1 Disperse Blue 14 (61500), C1 Disperse Blue 6 (62050) and Cl Disperse Blue 31 (64505 as direct dyes, Cl Direct Blue 2 (22590), C] Direct Black 51 (27720) and Cl Direct Violet 51 (27905); and as solvent dyes, (15680) and Cl Solvent Violet 10 (45190).

The surface-active agents of the present invention are also usefully used in hair rinses. These hair rinses are employed on the hair in order to make easier its dis-' entanglement, especially when same is electric or curly. These hair rinses comprise a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol such as ethanol and isopropanol wherein said alkanol is present in amounts of about 15 to 60% by weight of said solution, a cosmetic resin in amounts of about 0.5 to 5% and 0.1 to 2% by weight of surface-active agents of the present invention. This composition may also comprise a perfume in amounts of about 0.05 to 0.5% and hair dyes from an amount of about 0.005 to 3% of said composition which has a pH from about 7 to 8.5 Representative. cosmetic resins include polymers, i.e. polyvinyl pyrrolidone (PVP) having a molecular weight ranging between 40,000 to 360,000 the preferred molecular weight being 40,000, or copolymers such as the copolymer of polyvinyl pyrrolidone and vinyl acetate (MW 40,000 160,000) 70% 30% to 30% 70%, the preferred proportion being 60% 40% having a viscosity of 3,3 to 4 centipoises in 5% solution in ethanol; or copolymers of crotonic acid and vinyl acetate 10% having a molecular weight of 40,000 to 200,000 and preferably of 50,000 and a viscosity of 7 to 9 centipoises in solution in tetrachlorethane; or monoalkyl ester of the copolymer of methylvinyl ether and maleic acid.

Representative hair dyes include direct dyes such as azo dyes, triphenylmethane type dyes, xanthene dyes, anthraquinone dyes, azine dyes, premetallized dyes,

solvent dyes and the like. All the above cited dyes as.

commercially available useful dyes may be used.

in use, the compounds of the present invention can be in the form of salts of inorganic and organic acids such as hydrochloric, phosphoric, boric, acetic, citric and lactic acids.

II. Preparation of Surface-Active Agents Wich Are The Condensation Product Of An Alcohol And Glycerol Epihalohydrin EXAMPLE 1 in which n has a statistical average value of l.

371 g of this compound are dissolved in an equal weight of tertiary butyl alcohol and 148 g of an aqueous 40% solution of sodium hydroxide are added drop by drop, while stirring.

The temperature rises from 25 to 28C.

The mixture is then heated to 6570C while stirring.

After being cooled to ambient temperature, the sodium chloride precipitate is dissolved by adding 300 cm of water.

The aqueous phase containing the sodium chloride and the excess sodium hydroxide is drawn off.

The organic phase is left overnight, then filtered.

After evaporation of the tertiary butyl alcohol first under normal pressure, then under the vacuum of a water-jet pump, the glycidyl ether having the following formula is collected:

lCH

T 12 0 EC H (CH Cl)Oa-Cl- Gil /CH N CH -CHQH-CH In this formula n has a statistical average value of 1. This compound is water soluble in an acid medium.

222 g of this chlorinated amine are then heated with 46.6 g of potassium acetate in the presence of 260 g of dipropylene glycol at 180l85C for 3 hours.

The potassium chloride is separated by filtration, then the dipropylene glycol is evaporated in a vacuum.

In order to complete the de-acetylation, 166 g of the product are dissolved in 200 g of absolute ethyl alcohol. 1 cm of a 25% solution of sodium methylate in methanol is added and the mixture is left at ambient temperature for 18 hours.

The ethyl acetate formed and the alcohol, are evaporated, and 163.5 g of the compound having the following formula are collected: C H O "'EC. H (CH OH)oflacl-l CHOibCl-i -N CH -CHOHCH CH CHOH-CH Here n has a statistical average value of 1.

This product is in the form of a colorless viscous oil, soluble in water, with a pH less than or equal to 7, this pl-l being adjusted by adding lactic acid.

EXAMPLE 2 The process is the same as in Example l, except that the diisopropanolamine is replaced by diethanolamine. The polychlorinated tertiary amine having the following formula is prepared:

n having a statistical average value of l with a yield of about 93%.

After treatment with potassium acetate at l8l C in dipropylene glycol, filtration, evaporation of the dipropylene glycol and ethanolysis, the compound having the following formula is obtained:

Ca -0H n has a statistical average value of 1.

This compound takes the form of a viscous yellow oil, soluble in water and having a pH less than or equal to 7.5. It forms gels at a 4% concentration at a pH of 7.5 to 7.2 in an aqueous medium (the pH being adjusted with lactic acid).

EXAMPLE 3 4.5 moles of glycerol epichlorohydrin are reacted with 3 moles of a mixture of fatty alcohols containing about 55% dodecanol and 43.5% tetradecanol. The product is monoalkyl ether of polyepichlorohydrin having the formula: v

RO[-C H O(Cl-l CL)-};CH CHOl-lCH CI in which n has a statistical average value of 0.5 and R represents an alkyl radical with 12 to 14 carbon atoms.

This compound is then dehydrohalogenated according to the process described in Example 1.

Glycidyl ether having the following formula is obtained:

uct reacts with the diisopropanolamine at a 5% molar excess to form the tertiary amine:

R fC H (CH CDOQl CH -CHOH-CH CH2-CH0HCH CH CHOI-l-CH with a 94% yield.

Then, after treatment with potassium acetate at l80185C, dipropylene glycol being used as the solvent, filtration of the potassium chloride and evaporation of the solvent, the polyhydroxyl amine having the following formula is obtained:

/ CH -CHOHCH with n and R having the meaning given above.

EXAMPLE 4 The process is the same as in Example 3, except that the diisopropanolamine is replaced by diethanolamine in identical molar proportions. The chlorinated amine having the following formula is prepared:

CH --CH OH R is alkyl having 12-14 carbon atoms, n has a statistical average value of 0.5.

By hydroxylation at l80-l85C for 3 hours in dipropylene glycol, with a stoichiometric quantity of potassium acetate with respect to the chlorine, the polyhydroxyl amine having the following formula is obtained:

on ...N 2

in this formula R and n have the meaning given above.

EXAMPLE 5 By condensation of 2 moles of glycerol epichlorohydrin on one mole of a mixture of fatty alcohols identical to that used in Examples 3 and 4, the monoether of polyepichlorohydrin having the following formula is first prepared:

hol, glycidyl ether having the following formula is obtained:

In this formula R and n have the same meaning as above. Yield: 98.5%. Epoxide content: 100% of the theoretical value.

This product, when reacted at 95C with diethanolamine in a molar excess of 5% yields the chlorinated amine having the following formula:

again R and n have the meaning given above. Yield: 98%.

Potassium acetate at a molar excess of 10% is then substituted for the chlorine at ll85C, using a quantity of dipropylene glycol equal in weight to that of the chlorinated amine as the solvent.

The potassium chloride is removed by filtration and the solvent is evaporated in a vacuum.

The raw product, in which about 7% of the alcohol functions are esterified by acetic acid, is purified in the following manner:

The esters are saponified with an aqueous 14% solution of sodium hydroxide in stoichiometric proportions.

The hydroxyl amine is dissolved in an equivalent weight of butyl monoether of diethylene glycol. The organic phase is washed twice with boiling water, and the liquid is decanted while hot.

After removal of the water and solvent, a compound having the following formula is obtained:

wherein R and n have the meaning given above.

This product is a yellow-orange oil which is soluble in water at a pH of 7 (the pH being adjusted by the addition of lactic acid).

EXAMPLE 6 By using the same glycidyl ether as in Example 5, but

replacing the diethanolamine with morpholine in the.

same molar proportions, the chlorinated amine having the following formula is obtained:

OH I

2 I in this formula R represents an alkyl radical with 12 to 14 carbon atoms and n has a statistical average value equal to that of the filtrate is added and the mixture is heated to 70C. It separates into two phases.

The aqueous phase, containing the sodium acetate, is drawn off while hot.

The water and solvent are evaporated together from the organic phase by progressive elevation of the temperature to 180C under a pressure of 18 mm of mercury.

An orange oil is obtained.

This product has the following formula:

in which R represents alkyl having 12 to 14 carbon atoms and n has a statistical average value of l. The product is soluble in water which has been acidified with lactic acid to pH 6.3.

EXAMPLE 7 2 moles of epichlorohydrin are reacted with one mole of industrial oleyl alcohol. The monoether of polyepichlorohydrin having the following formula is obtained:

In this formula R represents the 9-octadecenyl radical, n having a statistical average value of 1.

After treatment with an aqueous solution containing 40% sodium hydroxide at an excess of 50% in the presence of tertiary butyl alcohol, this yields the corresponding glycidyl ether.

Yield: 98%. I Expoxide content: 98% of the theoretical value.

The tertiary chlorinated amine having the following formula with R and n having the meaning given above, is prepared by heating this epoxide with diethanolamine at a molar excess, the temperature being held at 95C for 2 hours.

Hydroxylation is then carried out as described above, with potassium acetate and dipropylene glycol.

After filtration of the salt and evaporation of the solvent, the resultant product may be purified as follows:

200 g of the product are dissolved in 200 g of monobutylether of diethylene glycol.

The acidic esters are saponified by addition of a stoichiometric quantity of an aqueous solution containing 40% sodium hydroxide. Then 200 g of hot water are added, the mixture is stirred for several minutes, and the aqueous phase containing the sodium acetate is drawn off.

After evaporation of the water and solvent, 195 g of the product having the following formula are collected:

This compound is soluble in water at a pH of about 6.5, this pll-l being adjusted with lactic acid.

EXAMPLE 8 From the oleyl alcohol identical to that used in Example 7, the following compounds are successively prepared. First, the oleyl ether of polyepichlorohydrin having the formula:

RO-[-C l-l (CH Cl)O-l;Cl-l CHOHCH -Cl in which:

R 9-octadecenyl(oleyl), and

n has a statistical average value of 3, and then the corresponding glycidyl ether having the formula:

wherein R and n have the meaning given above.

By opening the epoxide with diethanolamine under the same conditions as before, the following chlorinated amine is obtained:

wherein R and n have the meaning given above.

This product is then dissolved in an equivalent weight of monobutylether of diethylene glycol and heated to l-l C for 3 hours with potassium acetate.

1.10 mols of potassium acetate are used per gramatom of chlorine.

The percent transformed, calculated on the basis of the consumption of the acetate, is about 98%.

The potassium chloride is separated by filtration. The solvent is then evaporated in a vacuum by progressively raising the temperature to C.

The raw product is dissolved in alcohol, decolorized with animal charcoal, then ethanolyzed with sodium methylate as a catalyst.

0.5 g of catalyst are used per 100 g of the product.

The alcohol and ethyl acetate which has formed are evaporated.

The polyhydroxylated amine having the following formula is obtained:

R 9-octadecenyl and n has a statistical average value of 3.

This is a very viscous oil which is soluble in water at 25C. The pH of a M/lO solution is about 9.3.

EXAMPLE 9 After reacting 264 g of Hexadecylic alcohol (sold commercially the Esso Corporation) with g of epichlorohydrin at 60C in the presence of 1.2 ml of an acetic acid complex of boron fluoride, a polychlorinated polyether having the following formula is obtained:

wherein n has a statistical average value of 1.

In 200 g of monobutylether of diethylene glycol at ambient temperature, the following are successively dissolved:

179.6 g of polychlorinated polyether and 46 g of diethanolamine at 96%.

Then, drop by drop, 44 g of an aqueous 40% solution of sodium hydroxide are added. The temperature of the reaction mixture rises to 32.

The mixture is stirred for 15 minutes first, at ambient temperature and then in a boiling water-bath for 1 hour.

A polychlorinated amine having the following formula is thus obtained: C H

CHCH O--'EC H (CH Cl)O3-5CH 8 17 CH -CH OH -CHOH-CH N wherein n has a statistical average value of 1.

This product is soluble in water in an acid medium.

The hydroxylation reaction is carried out as follows:

The excess sodium hydroxide is neutralized with 2.4 g of pure acetic acid. Then 31.8 g of anhydrous sodium acetate are added.

The mixture is heated to l85-l90C for 6 hours after the water has been removed by evaporation.

The sodium chloride is separated by filtration; then the acetic esters formed are saponified with 37.6 g of a 40% solution of sodium hydroxide.

After addition of 650 g of water, the mixture is heated to 90C.

When allowed to settle, the mixture separates into two phases. The aqueous phase containing the electrolytes is drawn off, then the solvent of the organic phase is evaporated.

180 g of the product having the following formula are CHOH-CH -N 2 wherein n has a statistical average value of 1.

This compound is a clear yellow oil and is soluble in water at a pH of 3.

The tertiary amines prepared in the preceding Examples may be transformed into quaternary ammonium salts. This may be done very easily, particularly by using methyl sulfate, as shown in the following example:

EXAMPLE 10 To 50 g of a polyhydroxylated tertiary amine having the following formula:

-- SO CH wherein R and n have the meaning given above.

Example 10 is repeated using, instead of methyl sulfate, essentially comparable amounts of ethyl chloride, ethyl bromide, methyl iodide, methyl paratoluylene sulfate and methyl methane sulfonate to obtain similar quaternary ammonium salts.

EXAMPLE 1 l The monoether of polyepichlorohydrin, having the following formula, is prepared by condensing 2 moles of glycerol epichlorohydrin on a molar equivalent quantity of a mixture of fatty alcohols identical to that used in Examples 3, 4 and 5:

In this formula: R represents alkyl having 12 to 14 carbon atoms, and n has a statistical average value of 1.

40.5 g of anhydrous diethylamine are added to 191 g of this product. Then 55.5 g of an aqueous 40% solution of sodium hydroxide are added to the mixture in CH -CH 5 minutes with stirring. The temperature rises from 25. to 31C. The reaction mixture is progressively heated to 90C in 35 minutes and is kept at this temperature for 1 hour.

After the electrolytes have been dissolved in 76 g of water, a chlorinated amine having the following formula is separated by salting out at 90C:

wherein R and n have the meaning given above.

After dehydration the product is 93% pure according to amino group determinations. The chlorine is substituted using potassium acetate in dipropylene glycol at' This process takes 3 hours. The raw product collected after filtration and evaporation of the solvent is deacetylated by saponification with sodium hydroxide and washed with an equivalent weight of water at.

8085C. After decantation and dehydration in a vacuum, a yellow-orange oil having the following formula:

is obtained.

c n 5 -N wherein R and n have the meaning given above.

This compound is soluble in water at a pH less than or equal to 6 (the pH being adjusted with lactic acid).

EXAMPLE 12 As in Example 7, a monoether of polyepichlorohydrin having the following formula is first prepared:

CH -CH wherein R and n have the meaning given above. This product is mixed with an equivalent weight of diethylene glycol and reacted with sodium acetate at l80-l 85C for 3% hours. This reactant is added as an aqueous solution, the water being removed from the reaction medium by evaporation. 1.05 moles of acetate are used per atom of chlorine to be replaced.

After removal of the salt by filtration and evaporation of the solvent, the product is a brown oil. It is soluble in water at a pH less than or equal to 4.5 (the pH being adjusted with lactic acid). It has the following formula: I

CH --CH wherein R and n have the meaning given above.

EXAMPLE 13 By the same process as in Example 12, except that morpholine is replaced by diisopropanolamine, a compound having the following formula is prepared:

CH -CHOH-CH equal to 5.5 (the pH being adjusted with lactic acid).

EXAMPLE 14 The procedure is the same as in Example 12, except that instead of using oleyl alcohol having an purity (as in Examples 7, l2 and 13), the first step is to prepare from an oleyl-cetyl alcohol sold under the trademark Ocenol l-lD-50-55" by the Dehydag Company, which is a commercial oleyl-cetyl alcohol, having an iodine index of 45-55, a chlorinated amine having the formula:

CH -CH wherein R represents a hydrocarbon radical having 12 to 18 carbon atoms, and n has a statistical average value of l.

The chlorine is then substituted using potassium acetate in dipropylene glycol as a solvent.

CH CH Du ration The product obtained after filtration and evaporation of the solvent has the following formula:

R0 40 1-1 (Cl-i OH)Ofl- CH -CHOH-CH CH -Cl'l2 I wherein R and n have the meaning given above.

Ocular tests on rabbits have shown it to be absolutely harmless when applied as an aqueous solution having a pH of 4 and an active product concentration of l/ 10 mole/liter.

EXAMPLE 15 The monoether of polyepichlorohydrin having the following formula is prepared by reacting 2 moles of epichlorohydrin with a molar equivalent quantity of 2- octyldodecanol (sold under the trademark EUTA- NOL-G) in the presence of 1.2 ml of an acetic acid complex of boron fluoride:

-CHOH-CH Cl wherein n has a statistical average value of 1.

This compound is then condensed with morpholine 3 60 in the presence of sodium hydroxide.

chlorohydrin 1.05

Molar proportion of sodium hydroxide:

The mixture is heated to C for 2% hours. A chlorinated amine having the following formula:

CHCH O -Ec H (CH Cl)i? CH 21 CH -CH 2 2 -CHOH-CH -N wherein n has the meaning given above and obtained after washing and dehydration, has an amine group content of 1.70 mEq/g.

The chlorine is then substituted by heating said amine at l80l85C with a 5% excess of anhydrous potassium acetate with respect to the quantity theoretically necessary. Dipropylene glycol is used as the solvent. The process takes 4 hours.

After filtration and evaporation of the dipropylene glycol, the acetic esters are saponified with an aqueous 40% solution of sodium hydroxide. Then the product is washed with a mixture of equal weights of water and methanol.

A polyhydroxylated amine having the following formula:

CH-CH O -EC H CH OH O-Zl CH on -CH 2 2 -CHOH-CH2-N in which n has a mean statistical value of 1, is obtained in the form of a yellow-orange oil.

EXAMPLE 16 The monoether of polyepichlorohydrin, having the following formula, is prepared by reacting 3 moles of glycerol epichlorohydrin with 0.5 mole of nonylphenol in the presence of 0.85 ml of acetic of boron fluoride at 7085C:

-CHOHCH Cl C H OH The chlorine is then replaced as follows: The sodium hydroxide remaining in the reaction mix- 'ture is neutralized with acetic acid. The mixture is heated to 180l C and 0.5 mole of aqueous sodium acetate is added in 45 minutes. The water is removed by evaporation. After an hour of heating at l80l85C, 45.1 g of an aqueous 40% solution of sodium hydroxide are added in 1% hours, and the sodium acetate is thus recovered from the acetic esters previously formed. The temperature is kept at l80-l85C for 2% hours after the sodium hydroxide has been added. After cooling, the salt is removed by filtration and the diethylene glycol is evaporated under reduced pressure. A polyhydroxylated amine having the following formula is obtained:

-CHOH-CH -N In this formula n has a statistical average value of S.

The product is soluble in water at apl-l of 9 and in a 10% sodium hydroxide solution.

EXAMPLE 17 By proceeding as in Example 16, except that the diethanolamine is replaced by morpholine, a polyhydroxylated amine having the following formula is prepared:

EXAMPLE 18 An alcohol having an average molecular weight of 290 is prepared by catalytic reduction, in the manner,

conventionally used to reduce fatty alcohols, of the isostearic acid sold commercially by the Emery Company.

The isostearic acid used has the following properties:

Iodine index 10 Saponification index 5.6 Titer l0 By reacting 0.3 mole of alcohol with 0.6 mole of epichlorohydrin in the presence of 0.4 ml of an acetic acid complex of boron fluoride at 70-75C, a polychlorinated polyether having the following formula is obtained:

wherein R represents an alkyl radical derived from isostearic acid, and n has a mean statistical value of l.

60 g of the clear yellow oil which results is mixed with 19 g of diisopropanolamine. Then 14.5 g of an aqueous 40% sodium hydroxide solution are added.

After 1% hours of heating at C, the product is completely soluble in water in an acid medium. From a determination of the tertiary amines, the percentage of transformation is approximately The resulting chlorinated amine is now changed to a polyhydroxylated amine as follows:

polyhydroxylated amine having the following formula is obtained:

The following substances are successively added to H the reaction mixture: 2 3 2 n 2 0.8 ml of glacial acetic acid, 5 2' 3 120 g of dipropylene glycol, and

1 1.45 g of anhydrous potassium acetate.

The mixture is heated to l80185C for 6 hours. wherein R represents a hydrocarbon radical derived After cooling the salt is removed by filtration and the from isostearic acid, and n has a statistical average dipropylene glycol is evaporated under reduced presvalue of l. sure. The compound is a straw-yellow oil.

The resulting product, whose saponification index is Examples 19-28 which illustrate the preparation of 5.6, is treated with l g of an aqueous 40% sodium hyadditional surface active agents in accordance with this droxide solution, then washed at 95C with 70 g of waembodiment of the present invention are set forth ter. After decantation and drying in a vacuum, a below in Table 1.

TABLE 1 Step (a) Hydroxyl Index 01' Example Glycerol Resulting Polyhalogenated No. Alcohol Catalyst Epichlorohydrin Polyether R (Grams) Moles BF /C(H lCOOH (Grams) Moles n +1 Found Theoretical l9 cetyl/ 143 0.5 1.5 462.5 5 10 57-58 46 stearyl 532 2.1 2.2 370 4 1.9 128 131 2| H 23 *residue of 410 2 3 832 9 4.5 95.5 90.5

Dobanol Z4 Hexadecyl 132 0.5 0.8 185 2 4 95 88 Nonylphenyl 220 l 1 185 2 145 138 g; 1: 1 9- 9- 1: 1: '2 28 220 l 1 185 2 2 145 138 Dobanol (Shell) Mixture of saturated principally straight chained aliphatic alcohols having 1 l-15 carbon atoms 14'71 branched chained).

TABLE I (Contd) Step (b) Step (0) Polyhalogenated NaOH Example Polyether Reaction No. (from Step a) soln.) Secondary Amine Time (Grams) Moles (Grams) Nom (Grams) Excess (Hours) 19 200 0.2* 22.8 Piperidine 23 5 1.5 20 214.5 0.49 54 Mo holine 44.7 5 21 200 0.45 Diet anolamine 50.8 5 22 Diisopropanolamine 65.5 5 23 1200 2.09 219 Diethanolamine 244 10 2 24 190 0.3 50 Morpholine 27.5 5 2 25 202 0.5 Dicthanolamine 57.5 5 2.5 26 0.24 25.4 28.2 10 1.5 27 Morpho1inc** 23.2 10 3 28 0.33 36.3 Morpholine*** 30.2 5 1.5

200 g dipropylcnc glycol added as solvent 11 10 g dipro'pylcnc glycol added as solvent 150 g tcrtiobutyl alcohol added as solvent TABLE 1 (contd) Step (d) Alcoholysis Potassium Time At Absolute Ethyl Saponifi- Solvent Acetate CH COOH NaOH 40% C. Alcohol cation Salting Out NaOH-40% Soln. No. Type (Grams) (Grams) (Grams) (Grams) (Hours) trace MeONa (Grams) (in water) 19 DPG 400 148.5 6 20 DEG 300 26 43.5 3 21 24.6 41 4.5 ith BDG 22 320 24.6 41 3 23 DEG 1200 720 6 TABLE I (cont'd) Step (d) Alcoholysis Potassium Time At Absolute Ethyl Saponifi- Solvent Acetate CH3COOH NaOH 40% 185C. Alcohol cation Salting Out NaOH-40% Soln. No. Type (Grams) (Grams) (Grams) (Grams) (Hours) +trace MeONa (Grams) (in water) 24 BDG 206 93 s 72 25 DEG 300 30 47 5 26 36.8 6L2 3.25 27 I80 30.8 01 3 28 150 23.8 40 3 DEG Diethylene glycol BDG hutyl digylcol DPG Diprupylenc glycol MeONa sodium methyl-ate TABLE I 2. agents which are the quaternary ammonium salts of (1) having the formula (Contd) 2O 1 d ofH gnalyiisr d 1 d of solubmty n 8X I'OX ae l'l 6X Amine om c sa onm acidified R'O-E )o3; -E H H H o-3;c11 Invention cation Water Example Found No. (meq/g) Theoretical Found* 19 R ii is 'ii I CHOH CH N 1 Y 0 2 22 1.85 1.89 0.17 23 0.39 24 1.65 L60 0 25 1.9 L80 0.38 (Cloudy) 5; :3; Q 8-3 1 wherein R,R, R R m and n have the meaning given 23 1:94 1,3 1 above, R is selected from the group consisting of I methyl and ethyl and Y is an anion selected from the Theoretical Index Of Supomficauon =0 g p consisting of I SO4CH3 SO4C2H5 CH SO and Ill. Surface Active Agents Which Are The Condensation Product Of An Alcohol, An Epoxide And Glycerol Epihalohydrin In accordance with this embodiment of the present 40 The canon: surfajce actfve agents of thls embod" invention there is provided cationic surface-active of the Present mvemlon are prepfred by agents Selected from the group consisting a. condensing on a fatty alcohol havmg the formula agents having the formula R'OH wherem R has the meaning given above, m I C C moles of an epoxide or mixture of epoxides having the R O-EC H (R )OEl-EC H H OIUO-Il- H formula I ll R R C? 7H -CHOH-N (VI 0 2 wherein R has the meaning given above to form a corn ound havin the formula which are hydroxylated condensation products of an p g alcohol having the formula R'OH, an epoxide having RO[-C H (R")O-} l-l the formula Wm);

R"-CHC 2 b. condensmg on the compound represented by formula Vlll, (n+1) moles of glycerol epihalohydrin havand glycerol epihalohydrin, wherein R is a hydrophilic mg the formula group selected from the class consisting of linear or CH H-CH branched alkyl and alkenyl having 12-20 carbon atoms, R" represents a member selected from the group consisting of methyl and ethyl, m has a statistical Whefelfl has the e ng gl en above and X is haloaverage value of 2-6, R, and R each independently ar gen, preferably chlorme or bromine to form a mixture selected from the group consisting of lower alkyl hav- 0 polyhalogenated polyethers having the formula ing l-4 carbon atoms, lower hydroxyalkyl having 1-4 carbon atoms or together with the nitrogen atom to which they are attached form a ring selected from the group consisting of morpholine and piperidine and n has a statistical average value of 0.5-4; and

c. dehydrohalogenating said polyhalogenated polyethers from step (b) with an alkali metal or an alkaline earth metal hydroxide to form a mixture of polyhalogenated glycidyl ethers having the formula d. reacting the polyhalogenated glycidyl ethers from step (c) with a secondary amine to form a mixture of polyhalogenated tertiary amines having the formula -CHOH-CH (XI) 3 and (e) replacing the halogen by hydroxyl in the polyhalogenated tertiary amines from step (d) to form a mixture of polyhydroxylated tertiary amines having formula VI given above.

The various steps in the above process for preparing the surface active agents represented by formula VI are as follows:

-CH -CH-O and CH X and I is the hydroxyl index of the condensation product, i.e., the compound represented by formula VIII above, after step (a).

(VIII) The quaternization of the surface-active agents represented by formula VI yields quaternary ammonium 50 salts having the formula A B Y -CHOH-CH2 (VII) wherein R',R, R R R Y, m and n have the meaning given above.

In the course of the condensation reaction (a) and (b) above, when the epoxy ring is opened during the polycondensation, a mixture of compounds comprising the structure In the same formula above, n is defined by the equation:

wherein M is equal to the molecular weight of the alco- 5 hol of formula VIII, E is equal to the molecular weight of the glycerol epihalohydrin and I is the hydroxyl index of the condensation product, i.e., the mixture of polyhalogenated polyethers represented by formula IX, after step (b).

During the condensation reaction (a) in which m moles of the epoxide having formula R"-CH-7H I which epoxide can be for instance propylene oxide and/or butylene oxide, are reacted on one mole of alcohol having the formula R'OI-I, the number of moles of epoxide fixed by one mole of alcohol to form the recurring units -[-C H (R")O-l can be greater or smaller than the value m and a mixture of compounds, all responding to general formula VIII are formed, but in which the number of recurring units varies and all those different numbers are distributed statistically around a mean value represented by m. Consequently m in the final product represents the mean value or the average statistical value of the number of recurring units -E-C H (R' ')O] fixed on the different compounds having the general formula (VI) or VII.

During the condensation reaction (b) in which (n+1) moles of glycerol epihalohydrin are reacted on one mole of alcohol RO-[-C H (R")O-]-l-I designated as formulga VIII the number of moles of glycerol epihalohydrin fixed by one mole of alcohol VIII to fonn the recurring units -{-C H (CI-I OH)O-}- can be greater or smaller than the value n and a mixture of compounds, all responding to general formula IX are formed, but in which the number of recurring units -{-C l-l (Cl-l OI-I- )O-lvaries and all those different numbers are distributed statistically around a mean value represented by n. Consequently n in the final product represents the mean value or the average statistical value of the number of recurring units [-C I-l (CI-I Ol-I )O-}- fixed on the different compounds having the general formula VI or VII.

An important fact which sould be emphasized and which constitutes one of the essential advantages of the process of preparing the surface-active agents of this invention is that the present process results in the formation of compounds having a single lipophile chain per hydrophile chain.

Moreover, the process of the present invention permits the regulation of the hydrophilic and lipophilic properties of the final product. The hydrophilic characteristic of the resulting surface-active agents can be regulated by choosing the value of the number n of moles of glycerol epihalohydrin reacted with one mole of fatty alcohol. The lipophilic characteristics of the resulting surface-active agents can be regulated by choosing the length of the hydrocarbon chain R in the fatty alcohol.

The following is a detailed description of a preferred embodiment of producing the above surface-active agents.

In steps (a) and (b), i.e., the condensation of propylene and/or butylene oxide on one hand and of glycerol epichlorohydrin or epibromohydrin on the other hand, are carried out, one after the other, in the presence of an acid catalyst such as boron trifluoride, stannic chloride or antimony pentachloride, at a temperature of between 25 and 160C and preferably between 60 and 120C if boron trifluoride is used. The proportion of BF with respect to the total mass of the reactants is between 0.1 and 1% by weight.

In step (c) the polyhalogenated polyethers represented by formula (IX) above, which result from step (b), are converted to glycidyl ethers (formula X) by dehydrohalogenation of the halohydrin, using an aqueous solution of an alkali or alkaline earth metal hydroxide, having a concentration, by weight, of from to 50%. The molar ratio of alkali or alkaline earth metal hydroxide to polyhalogenated polyethers ranges between 1:1 and 1:2 and preferably from about 1:1.2 to l:l.5. During this phase of the overall process, which ordinarily is initially conducted at about 20C or ambient temperature, the reaction temperature rises to about 100C. When the exothermicity of the reaction ceases,

the reaction is terminated by heating the reaction mixture in a water bath. This dehydrohalogenation operation is generally conducted in the presence of a solvent to obtain high reaction speeds and high epoxidation yields. The solvent employed should preferably, not be miscible with concentrated aqueous solutions of electrolytes so that the resulting polyhalogenated glycidyl ethers can be separated from the reaction medium simply by decantation. Tertiary butyl alcohol and 2-butoxy ethanol are particularly useful solvents when used in weight proportions essentially equal to that of the halohydrin to be dehydrohalogenated. Quaternary ammonium salts comprising a lipophile chain can be used to improve the contact between the reactants. The resulting polyhalogenated glycidyl ethers if desired, can be isolated by evaporation of the solvent or it can be used in solution in the subsequent stage, i.e., step (d).

In a step (d) the polyhalogenated glycidyl ethers from step (c) are reacted with a secondary amine at temperatures of from 25 to C to open the epoxide ring and thereby form the polyhalogenated tertiary amines having formula XI.

Alternatively the polyhalogenated tertiary amines of formula Xl can be obtained in a single step by reacting the polyhalogenated polyethers from step (b) directly with a secondary amine in the presence of an alkali or alkaline earth metal hydroxide.

Representative secondary amines usefully employed in the present invention include diethylamine, dipropylamine, morpholine, piperidine, and alkanolamines such as diethanolamine, diisopropanolamine, diglycerylamine and N-ethylethanolamine.

The molar ratio of secondary amine to epoxide (when the glycidyl ethers responding to formula IX are isolated) and the molar ratio of secondary amine: halohydrin (when the secondary amine is reacted directly without isolating the glycidyl ethers responding to formula IX) are between about 1:1 and 111.5, the preferred ratio being about l:l.5.

In step (e) the replacement of the halogen by a hydroxyl in the polyhalogenated tertiary amine from step (d), or from its alternate route, yields the polyhydroxylated amines of the present invention which are useful surface-activeagents and which are represented by formula VI. This operation is carried out with an alkaline salt of carboxylic acid, such as sodium or potassium ac-- 50- a solvent.

The pressure of a solvent in the reaction medium durcontact among the reactants and easy separation therefrom of the mineral halide formed. Suitable solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, as well as the monoalkylethers of these diols, such as monobutyl ether of ethylene glycol and monobutyl ether of diethylene glycol. The hydroxylated solvents also intervene by alcoholysis of the; esters formed in an intermediate step.

When the reaction is carried out in the absence of a solvent, as may be the case when the alkaline salt of carboxylic acid is somewhat soluble in the reaction medium, the polyhydroxylated tertiary amine is obtained by alcoholysis of the esters of carboxylic acid with a lower alcohol such as methanol or ethanol, or by saponification followed by salting out or extraction.

In one preferred commercial embodiment, the polyhalogenated polyethers from steps (a) and (b) are re-' acted with a secondary amine, as defined above in the presence of an alkali or alkaline earth metal hydroxide, without isolating the glycidyl ethers thus formed. After reaction with an alkaline salt of carboxylic acid, the esterified amino ethers are separated from the mineral halide by filtration or washing, and then the salts of carboxylic acid are regenerated in situ from the carboxylic esters by saponification with an alkaline hydroxide. Thus, the alkaline salt of carboxylic acid is recovered in aqueous solution and can be used for another hydroxylation reaction.

As stated above, the surface-active agents of this embodiment of the present invention also include the quaternary ammonium salts of the compounds represented by formula VI, the quaternary ammonium salts being represented by formula VII. To produce said quaternary ammonium salts, the compounds represented by formula VI can be reacted with, for instance, a quaternizing agent such as methyl sulfate, ethyl sulfate, ethyl chloride, ethyl bromide, methyl iodide, methyl paratoluylene sulfate or methyl methane sulfonate. The mole ratio of quaternizing agent to the compounds represented by formula Vl corresponds to the stoichiometric amount or is slightly inferior and the reaction is carried out at a temperature ranging from about to 100C at atmospheric pressure.

Compared, for example, with fatty amines, the surface-active agents of this embodiment of the present invention lack the odor characteristic of fatty amines and their derivatives, have a low melting point, are saturated and consequently do not become rancid.

Additionally, the process of the present invention yields stable surface-active agents which are soluble in water without the introduction of supplementary ionic groups, and especially anionic groups which impair the substantive characteristics of the surface-active agents. Further, the surface-active agents of this invention are considerably less irritating to the skin and to mucous membranes than are the fatty amines and their deriva- 1 tives.

The surface-active agents of the present invention also compare favorably with amino polyethers having the formula R1 R(OCH CH N and the substitution of a -{-C H (CH OH)O-}- group for the oxyethylene group (-OCH CH is very useful.

The surface-active agents of this invention, because of their physical and chemical characteristics, are suitably employed in cosmetic preparations, shampoos, permanent waving compositions and particularly in hair dye and hair rinse compositions. Further, when the surface active agents of this embodiment of the present invention, and especially those represented by formula VI are used in compositions for treating hair, they impart to the hair a certain sheen and a pleasing texture. The hair is particularly soft, odorless and is easily un tangled.

Thus, in accordance with the present invention there is provided a shampoo composition comprising an aqueous solution of the surface active agents of this invention present in amounts of about 0.5 to 6% by weight of said shampoo composition, having a pH ranging from about 3 to 6.5. The pH can be adjusted to the desired value by incorporating into said composition an acidic component such as lactic, acetic or citric acid I and the like.

In another embodiment of the present invention hair is permanently waved by applying to the hair wound on curlers during the first stage, i.e., during the reducing stage, a composition comprising reducing agent, permitting the composition to remain on the hair for a time sufficient to alter the disulphide bonds of the keratin of the hair, generally about 10-40 minutes, thoroughly rinsing the hair to remove residual reducing agent and applying in the second stage, i.e., during the neutralization stage, a cosmetic composition comprising a mixture of an oxidizing or neutralizing agent and the surface-active agent of the present invention, whereby the disulphide bonds of the keratin of the hair are reformed.

Conventional reducing agents employed are advantageously those organic thiols which are generally used to perform the first stage of a permanent waving operation. Representative thiols include thioglycolic acid and its salts, glycol thioglycolate, glycerol thioglycolate, thioglycolic amide, thiolactic acid, glycol thiolactate, B-mercaptoethanol, N-carboxymethyl mercapto acetamid, B-mercapto propionic acid, and the like. Generally the composition comprising the reducing agent in an aqueous solution of said reducing agent present in amounts of about 2 to 15 percent by weight thereof and having a pH ranging from about 8 to l0.

The neutralizing composition of the present invention comprises an aqueous solution of 0.5 to 4 weight percent of a conventional neutralizing or oxidizing agent and about 0.2 to 15 weight percent of the surface-active agent of this invention. Conventional neutralizing agents employed include, for instance, hydrogen peroxide, sodium or potassium bromate, sodium perborate or percarbonate and the like.

The surface-active agents of the present invention are also usefully employed in hair dye compositions comprising a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol such as ethanol and isopropanol of a glycol such as butyl glycol, propylene glycol, ethylene glycol, 3-amyloxy 4-propane l,2-diol and of a monoalkyl ether of glycol such as monobutyl ether of ethylene glycol wherein said alkanol and/or glycol and/or ether of glycol is present in amounts of about 8 to 25 percent by weight of said solution, a hair dye such as azo, anthraquinone and nitro dyes of the benzene series, and 0.5 to 6 percent by weight of the surface-active agent of the present invention.

Additionally, if desire, said hair dye composition can include its weight of hydrogen peroxide to provide said composition in gel form.

Generally the dye is present in amounts of about 0.1 to 5 percent by weight of said composition which has a pH ranging from about 8 to 10.5.

Representative dyes include paraphenylene diamine, 2,5-toluene diamine sulfate, chloroparaphenylene diamine sulfate, nitroparaphenylene diamine, 1,2,4- triaminobenzene trihydrochloride, paraaminodiphenyl amine, ortho phenylene diamine, 4-chloro ortho phenylene diamine, 4-nitro ortho phenylene diamine, paraaminophenol, 4-amino 2-methyl phenol sulfate, 4-amino-3-methyl phenol, 4-amino 2-nitro phenol, mdiamino anisol and its sulfate, p-aminophenol and its sulfate, nitro-p-phenylene diamine, p-toluylene diamine, resorcine, hydroquinone. 3-nitro 4-B- aminoethylamino anisole hydrochloride, 2-4- diaminophenol hydrochloride, paramethyl aminophenol sulfate, ortho aminophenol, 4-chloro 2- aminophenol, 4-nitro 2-aminophenol, S-nitro 2- 31 aminophenol, 4,6-dinitro 2-aminophenol, 6-chloro 4- nitro Z-aminophenol hydrochloride, 4-amino diphenylamine, 4,4'-diamino diphenylamine sulfate, metaphenylene diamine, chloro-meta phenylene diamine, nitrometa phenylene diamine, meta toluylene diamine, 2,4- diamino anisol sulfate, metal aminophenol, 3,5- diaminophenol hydrochloride, diethyl meta aminophenol, paraamino ortho cresol, l-dimethylamino 3-amino ethylamino 4-nitro benzene, l-hydroxy-2,4-di(p-trimethylammoniumphenylamino) anthraquinone methosulfate, l-hydroxy-2,4-di (p-trimethylammoniumphenylamino) anthraquinone iodide, 1-

amino propylamino anthraquinone, 1,8-Bis-y -amino-,

propylamino anthraquinone, l-diethylamino 2- ethylamino-nitro-4-NN-dihydroxyethylamino benzene dihydrochloride, 4-N-methylamino-3-nitrol -N-B- aminoethylamino benzene, [l-hydroxy-4-(y methylmorpholinium) propylamino anthraquinone]methyl sulfate, 2-B-aminoethylaminoanthraquinone, 1,5-di-( B- aminopropylamino) anthraquinone, l-methylamino-4- amino propylamino anthraquinone, l-amino propylamino-anthraquinone 1,4-diamino-5-y aminopropylamino-anthroquinone. Additional examples of commercially available useful dyes include, as monoazo dyes, Cl Acid Blue 92 (13390) and Cl Acid Yellow 23 (19140); as diazo dyes, Cl Acid Orange 24 (20170); as triphenylmethane type dyes, Cl Acid Blue 1 (42045), Cl Acid Violet 19 (42685), Cl Acid Blue 22 (42755) and Cl Acid Violet 15 (43525); as xanthene dyes, Cl Acid Violet 9 (45190); as azine dyes, Cl Acid Black 2 (50420), Cl Acid Blue 59 (50315) and Cl Acid Blue 61 (50330); as anthraquinone dyes, Cl Acid Violet 43 (60730), Cl Acid Blue 80 (61585), Cl Acid Violet 51 (62165) and Cl Acid Blue 138 (62075); as premetallized dyes, both 1:1 and 2:1 complexes, chromium and cobalt, for instance Cl Disperse Blue 14 (61500), Cl Disperse Blue 6 (62050) and Cl Disperse Blue 31 (64505); as direct dyes, Cl Direct Blue 2 (22590), Cl Direct Black 51 (27720) and C1 Direct Violet 51 (27905); and as solvent dyes, (15680) and Cl Solvent Violet (45190).

The surface-active agents of the present invention are also usefully used in hair rinses. These hair rinses are employed on the hair in order to make easier its disentanglement, especially when same is electric or curly. These hair rinses comprise a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol such as ethanol and isopropanol wherein said alkanol is present in amounts of about to 60% by weight of said solution, a cosmetic resin in amounts of about 0.5 to 5% and 0.1 to 2% by weight of surface-active agents of the present invention. This composition may also comprise a perfume in amounts of about 0.05 to 0.5% and hair dyes from an amount of about 0.005 to 3% of said composition which has a pH from about 7 to 8.5 Representative cosmetic resins include polymers, i.e. polyvinyl pyrrolidone (PVP) having a molecular weight ranging between 40,000 to 360,000 the preferred molecular weight being 40,000, or copolymers such as the copolymer of polyvinyl pyrrolidone and vinyl acetate (MW 40,000 160,000) 70% 30% to 30% 70%, the preferred proportion being 60% 40% having a viscosity of 3,3 to 4 centipoises in 5% solution in ethanol; or copolymers of crotonic acid and vinyl acetate 90% 10% having a molecular weight of 40,000 to 200,000 and preferably of 50,000 and a viscosity of 7 to 9 centi- 1V. Preparation Of Surface-Active Agents Which Are The Condensation Product Of An Alcohol, An Epoxide And Glycerol Epihalohydrin EXAMPLE 29 Preparation of a mixture of surface-active agents having the formula CH -CHOH-CH -CHOH-CH CH 2-CH0H-CH3 wherein R is octadecyl, m has a statistical average value of 5.25 and n has a statistical average value of 1.

Steps (a) and (b) Poly addition of propylene oxide and glycerol epichlorohydrin on stearoyl alcohol 6.25 ml of an acetic acid complex of boron fluoride at 36% BE, are added to a molar equivalent quantity of industrial stearoyl alcohol (hydroxyl index: 195 mg KOH/g) dehydrated by heating in a boiling water bath in a vacuum and melted.

The mixture is heated to -80C. Then 5.25 moles of propylene oxide are added drop by drop, the rate of flow being regulated so that the temperature stays between 7580C because of the exothermic nature of the reaction. When the propylene oxide has been completely used up, which is determined by measurement of the epoxide function in a sample withdrawn for the purpose, 2 moles of glycerol epichlorohydrin are added drop by drop. The temperature is kept constant as before by regulating the rate of addition. The polychlorinated polyether having the following formula is obtained:

RO-[-C H (CH )O-1;,[-C H (CH Cl)O-l Cl-l CHOH-Cl-hCl, wherein R, m and n have the meaning given above, the said polyether having a theoretical hydroxyl index of 73.5(found mg KOl-l/g.

Steps (c) and (d) dehydrohalogenation and reaction with a secondary amine 177 g of diisopropanolamine, then 143 g of a 40% sodium hydroxide solution are added to 776 g of the wherein R, m and n the meaning given above.

Step (e) hydroxylation The excess sodium hydroxide is neutralized with 8 ml of anhydrous acetic acid. 800 ml of butyl monoether of diethylene glycol and 108 g of potassium acetate are added. After the water has been removed, the mixture is heated to l80-l85C for hours.

After cooling to 95C, 1.8 liters of hot water are added, the mixture is stirred and decanted and the aqueous phase containing the sodium chloride which has formed is drawn off.

The water and solvent are evaporated from the organic phase by progressively raising the temperature to 180C under a pressure of to mm of mercury.

An oily yellow product is obtained which is soluble in warm water at a pH of 3 (the pH being adjusted with lactic acid). Its formula is given at the top of this example.

This product can also be obtained with the same results by using the same reactant in the same proportions, but no solvent. In this case, the product is deacetylated by saponification, then separated by salting out.

EXAMPLE 30 The procedures of Example 29 are repeated except that comparably equivalent amounts of butylene oxide are employed in steps (a) and (b) rather than propylene oxide.

EXAMPLE 31 The procedures of Example 29 are repeated except that comparably equivalent amounts of glycerol epibromohydrin are employed in steps (a) and (b) rather than glycerol epichlorohydrin.

EXAMPLES 32-38 The procedures of Example 29 are repeated except that comparably equivalent amounts of diethylamine (Ex. 32), morpholine (Ex. 33), Piperidine (Ex. 34), diethanolamine (Ex. 35), dipropylamine (Ex. 36), diglycerylamine (Ex 37) and N-ethylethanolamine (Ex. 38) are employed in step (d) rather than diisopropanolamine.

EXAMPLE 39 A mixture of surface-active agents having the following formula is prepared: R O-EC 2H3( C l-l O- [-C 2H3 CH2C1) O-TI-HCH2 (H CH 2 2 wherein R is alkyl having 16-18 carbon atoms, m has a statistical average value of 3 and n has a statistical average value of l.

Proceeding as in Example 29, in steps (a) and (b) there are employed rather than stearoyl alcohol and propylene oxide, a mixture of fatty alcohols containing essentially cetyl alcohol and'stearyl alcohol having the following properties: hydroxyl index, 21 l; iodine index, 0.5 and fusion point, 525C; and butylene oxide, respectively, to produce the following polychlorinated polyether, R'O--C l-l (C H )O--C H (Cl-l C- l)O--CH CHOHCH Cl wherein R, m and n have the meaning given above.

Then, 36.5 g of morpholine and 44 g of a 40% aqueous solution of sodium hydroxide are added to 222 g of the above polychlorinated polyether. The addition of the sodium hydroxide takes 15 minutes and the resulting mixture is then heated in a water bath for 3 hours.

A polychlorinated tertiary amine having the following formula is thus obtained,

The excess sodium hydroxide is neutralized with 2.4 g of glacial acetic acid and the reaction mixture is diluted with an equivalent weight of dipropylene glycol. Then 35 g of anhydrous potassium acetate are added and the mixture is heated to ll85C for 5 hours after the water has been removed.

After evaporation of dipropylene glycol under reduced pressure, the de-acetylation is completed by saponification using 5 g of an aqueous 40% solution of sodium hydroxide. It is then washed twice with 250 ml of boiling water and the organic phase is then dehydrated by being heated in a vacuum. 211 g of a redbrown oil, having the formula given at the beginning of the example, are collected.

EXAMPLE 40 Preparation of a mixture of surface-active agents having the formula /CH -CH OH -caoH-eii -u CH CH wherein R is dodecyl, m has a statistical average value of 2 and n has a statistical average value of 4.

-CHOH-CH 0.8 ml of an acetic acid complex of boron fluoride at 36% BB, are added to 0.2 mole (37.2 g) of industrial dodecyl alcohol.

The mixture is heated to 75-80C. Then 0.4 mole of propylene oxide are added drop by drop, the rate of flow being regulated so that the temperature stays between 7580C because of the exothermic nature of the reaction. When the propylene oxide has been completely used up, which is determined by measurement of the epoxide function in a sample withdrawn for the purpose, 1 mole (92.5 g) of glycerol epichlorohydrin is added drop by drop. The temperature is kept constant as before by regulating the rate of addition. The polychlorinated polyether having the following formula is obtained:

Cl-lOl-l-Cl-bCl, wherein R, m and n have the meaning given above, the said polyether having a theoretical hydroxyl index of 73 mg KOH/g.

Steps (c) and (d) dehydrohalogenation and reaction with a secondary amine 22.5 g of diethanolamine, then 22 g of a 40% sodium hydroxide solution are added to 0.2 mole 103 g) of the above polychorinated polyether.

When the reaction ceases to be exothermic, the mixture is heated to 95C for 2 hours.

A mixture of polychlorinated tertiary amines having the following formula is thus obtained:

H CH on -CHOH-CH -N' 2 2 CH CH OH 1 10 g of dipropylene glycol and 44 g of potassium acetate are added. After the water has been removed, the mixture is heated to l80-l85C for 4 hours.

The potassium chloride which has formed is eliminated by filtration and the dipropylene glycol is evaporated under vacuum.

In order to complete the de-acetylation the crude product is dissolved in 125 ml of absolute ethyl alcohol to which 1 ml of a 25% solution of sodium methylate in methanol has been added.

After one night at room temperature the product is filtrated. Alcohol and the ethyl acetate which has formed are drawn off.

A brown viscous oily product is obtained which is soluble in water and the formula of which is represented above.

EXAMPLE 40 A The procedures of Example 40 are repeated except that comparably equivalent amounts of butylene oxide are employed in steps (a) and (b) rather than propelene oxide.

EXAMPLE 40 B The procedures of Example 40 are repeated except that comparably equivalent amounts of glycerol epibromohydrin are employed in steps (a) and (b) rather than glycerol epichlorohydrin.

EXAMPLES 40 C 40 J The procedures of Example 40 are repeated except that comparably equivalent amounts of diethylamine (Ex. 40 C), morpholine (Ex. 40 D), piperidine (Ex. 40 E), diisopropanolamine (Ex. 40 F), dipropylamine (Ex. 40 G), diglycerylamine (Ex. 40 H) and N- ethylethanolamine (Ex. 40 J) are employed in step (d) rather than diisopropanolamine.

Phosphoric acid Hydrogen peroxide, q.s.p. Water, q.s.p.

CH -CHOH-CH CH -CHOH-CH L2 g 7 volumes I cm It is noted that the application is simple, the lather goes on easily, it holds well on the curlers, rinses easily and after unrolling, the hair is particularly soft, shiny and odorless and untangles easily.

EXAMPLE 42 After reduction of the hair with an aqueous solution of the same composition as that above, the hair is rinsed and a solution having the following formula is applied as a fixative:

wherein R C -C and n has a statistical average value of 0.5.

Lactic acid, q.s.p. I pH 3.5 Hydrogen peroxide, q.s.p. 6 volumes Water, q.s.p. cm

It will be noted that, as above, the hair is soft, shiny and odorless, and that it combs out and untangles easily.

EXAMPLE 43 After reduction of the hair with a permanent waving composition having the following composition:

Thioglycolic acid 10 g Ammonium sesquicarbonate 10 g Ammonia, q.s.p. pH 8.5 Water, q.s.p. 100 cm wherein R C -C and n has a statistical average value of l.

Phosphoric acid l.5 g Hydrogen peroxide, q.s.p. 6 volumes Water, q.s.p. 100 cm After letting the setting agent act for a certain time, and rinsing, the hair is in very good shape, it untangles easily, is soft, and there is no foam left in it. These im-- provements in rinsing are due to the presence in the mixtures of the compounds that is the object of the present invention and to the fact that this mixture of compounds is highly hydrophilic due to the increase in the value of n from 0.5 to 1.

EXAMPLE 44 After using the same permanent waving composition as before, the following solution is applied as a fixativea g CH2CH2OH R {0 11 (CH 0H)Oi; CH -CHOH-CH -N 1. 5 5

CH3 a -cn -on so 0H wherein R is and n has a statistical average value of This gel is applied to the hair, left for 30 minutes, rinsed 0.5 and washed.

A chestnut shade is obtained.

C't 'd 0.l l-l yd i bg ii peroxide, q.s.p. 5 vo lumes EXAMPLE 46 Water, q.s.p. 100 cm .amigmchain alkylhaving l2 14 carbon A solution having the following composition is pre- 15 pared:

Nonylphenol oxyethylenated with l moles ethylene oxide g Nonylphenol oxyethylenated with 9 moles ethylene oxide 15 g;

Oleic acid 3 g H CH OH R0 +0 %(cn omoi -cn -cnon-cn -N 2 2 3 e;

The results are excellent. Rinsing is facilitated and wherein R is g'octadecenyl and n has a statistical aver softness of the hair is particularly pleasing. This is due age Value of to the fact that a quaternary derivative has been used instead of a tertiary as before, and this type of deriva- Butyl cfllosolve g tive has a greater affinity for hair and makes it softer 2 22 (sodium salt of ethylenediamine g and shlnler. tetracetic acid) Paratolylene diamine 1 8 Meta diamino anisol sulfate 0.05 g EXAMPLE Meta aminophenol 0.15 g. Para aminophenol OJ 8 A solutlon havmg the following composition is pre- 20% concentration ammonia 13 g pared: Water, q.s.p. cm

R0Ec H o(cH 0HH;H 5 a (R 9-octadecenyl Q has a statistical average value of 4) Oleic acid 3 g CH CH -OH RO-[-C H (CH OH)O-CH -CHOH-CH CH -CH -OH (R octadecenyl Q has a statistical value of 1)3 g Butylcellosolve 8 P;

Ethanol 8 Propylene glycol 5 E;

Trilon B (sodium salt of ethylenediamine O g tetracetic acid Paratolylenediamine l g Meta diamino anisol sulfate 0 .05 g

Meta aminophenol O .152; iPara aminophenol 0,1

20% ammonia 13 g Water, q.s.p. 100 cm To obtain the gel necessary for dyeing hair it is mixed To obtain a gel, the above mixture is further admixed with equal parts of hydrogen peroxide at 20 volumes. with equal parts of hydrogen peroxide at 20 volumes. 

1. A CATIONIC SURFACE-ACTIVE AGENT COMPRISING.
 1. A MIXTURE OF COMPOUNDS HAVING THE FORMULA
 1. A cationic surface-active agent comprising
 1. a mixture of compounds having the formula
 2. The surface-active agent of claim 1 having the formula
 3. The surface-active agent of claim 1 having the formula
 4. The surface-active agent of claim 1 having the formula
 5. The surface-active agent of claim 1 having the formula
 6. The surface-active agent of claim 1 having the formula
 7. The surface-active agent of claim 1 having the formula
 8. The surface-active agent of claim 1 having the formula
 9. The surface-active agent of claim 1 having the formula
 10. The surface-active agent of claim 1 having the formula
 11. The surface-active agent of claim 1 having the formula
 12. The surface-active agent of claim 1 having the formula
 13. The surface-active agent of claim 1 having the formula
 14. The surface-active agent of claim 1 having the formula
 15. The surface-active agent of claim 1 having the formula
 16. The surface-active agent of claim 1 having the formula
 17. The surface-active agent of claim 1 having the formula
 18. A cationic surface-active agent consisting of a mixture of compounds having the formula
 19. In a process for preparing a surface-active agent comprising a mixture of compounds having the formula
 20. In a process for preparing a surface-active agent comprising a mixture of compounds having the formula
 21. A cationic surface-active agent consisting of a mixture of compounds having the formula 